EP2986752B1 - Couche de protection contre l'oxydation à base de chrome - Google Patents

Couche de protection contre l'oxydation à base de chrome Download PDF

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EP2986752B1
EP2986752B1 EP14722542.9A EP14722542A EP2986752B1 EP 2986752 B1 EP2986752 B1 EP 2986752B1 EP 14722542 A EP14722542 A EP 14722542A EP 2986752 B1 EP2986752 B1 EP 2986752B1
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layer
chromium
individual
individual layers
oxidation protection
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EP2986752A2 (fr
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Juergen Ramm
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Oerlikon Surface Solutions AG Pfaeffikon
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Oerlikon Surface Solutions AG Pfaeffikon
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
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    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/347—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C28/44—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness

Definitions

  • the present invention relates to a chromium-based anti-oxidation layer for substrates which are exposed to high temperatures.
  • Oxidation protection layers are used, for example, in gas turbine parts, gas turbine blades, plates of combustion chambers or the like. There it is described how layers are applied to the substrates from a suspension by means of so-called plasma spraying. Such applied layers, however, have the disadvantage, among other things, that they can only be applied relatively thickly and also have tensions which can have a negative effect on the adhesion. Oxidation-resistant and poorly heat-conducting materials are also used in connection with pistons, for example in the DE10 2009 035841 disclosed.
  • the WO 2008/043606 A1 shows a PVD layer system for coating workpieces, which comprises a mixed crystal layer of a multiple oxide.
  • the WO 2006/099754 A1 discloses a hard material layer as an oxidic arc PVD functional layer which is deposited on a workpiece.
  • the layer is essentially designed as an electrically insulating oxide.
  • the EP 2 279 837 A1 shows an alternating layer system on a cutting tool of wood.
  • the object is achieved by a chromium-containing layer system according to claim 1.
  • the production method of the layer system is claimed in claim 4.
  • a layer system is applied by means of deposition from the gas phase.
  • PVD and / or CVD processes come into consideration here.
  • sputtering and / or evaporation under vacuum conditions can be used as the PVD method.
  • spark evaporation in which material is locally evaporated from a target surface by means of an electric arc.
  • a 3 ⁇ m thick CrN intermediate layer is applied to a substrate, to which a 3 ⁇ m thick AlCrO layer is applied.
  • the AlCrO layer can also be deposited as a multilayer layer, for example it can be deposited with different compositions for the individual layers.
  • a 3.5 ⁇ m thick CrN intermediate layer is applied to a substrate, onto which a 3.5 ⁇ m thick AlCrO layer is applied.
  • a 1.7 ⁇ m thick CrN intermediate layer is applied to a substrate, on which a 1.7 ⁇ m thick AlCrO layer is applied.
  • a 5 ⁇ m thick CrN intermediate layer is applied to a substrate, to which a 5 ⁇ m thick CrO / N multilayer (CrO / CrN multilayer) is applied.
  • the coating temperature can be 450C, for example.
  • a CrN / CrON multi-layer is applied to a CrN intermediate layer applied to the substrate (see the kalo section in FIG Figure 1 ).
  • the thickness of the CrN intermediate layer can be seen to be approx. 2.4 ⁇ m and the thickness of the multilayer approx. 3 ⁇ m.
  • the multilayer is a multilayer consisting of 36 individual layers, of which 18 CrN individual layers and 18 CrON individual layers (see Figure 1 ).
  • 18 CrN individual layers and 18 CrON individual layers see Figure 1 .
  • a coating temperature of approx. 230 ° C was maintained during the coating.
  • the number of individual layers and their thickness can be selected to suit the application.
  • the result is a thin, highly resistant protective layer that protects against oxidation, suitable, among other things, for substrates which are exposed to high temperatures in use and which should be protected against oxidation.
  • CrN was used as the intermediate layer.
  • other layers for example metallic chromium. It is also possible to first apply metallic chromium to the substrate surface, followed by a thicker CrN layer on which a CrN / CrON multilayer made up of thinner individual layers is then applied.
  • a chromium-based oxidation protection layer was disclosed for substrates which are exposed to high temperatures, the layer comprising a chromium-containing layer system which comprises a base layer and a functional layer and wherein the base layer is located between the substrate and the functional layer, and the base layer at least for the most part contains chromium nitride and the functional layer contains chromium oxide.
  • the base layer consists of chromium nitride, but can also consist of aluminum chromium nitride for some applications.
  • the functional layer contains at least for the most part aluminum chromium oxide or, preferably, the functional layer consists of aluminum chromium oxide.
  • the functional layer has a multilayer layer structure which comprises alternately deposited individual layers A and B, the composition of the A individual layers differing from the composition of the B individual layers.
  • the layer thickness of the base layer is preferably greater than 1 ⁇ m, for some applications it is preferably between 1.5 and 10 ⁇ m or, even more preferably, between 2 ⁇ m and 7 ⁇ m.
  • the ratio between the layer thickness of the functional layer and the layer thickness of the base layer is preferably between 0.5 and 2, or for some applications preferably between 0.25 and 1.5.
  • a chromium-based anti-oxidation layer for substrates that are exposed to high temperatures, the layer comprising a layer system containing chromium which comprises a functional layer, and the functional layer having a multilayered layer structure which comprises alternately deposited individual layers A and B, the composition of A.
  • Individual layers differ from the composition of the B individual layers, and the A individual layers contain at least for the most part aluminum chromium nitride or preferably chromium nitride and the B individual layers at least largely contain aluminum chromium oxide or chromium oxide or preferably aluminum chromium oxynitride or even more preferably chromium oxynitride.
  • the A individual layers contain at least for the most part aluminum chromium nitride or preferably chromium nitride and the B individual layers contain at least for the most part aluminum chromium oxide or chromium oxide or preferably aluminum chromium oxynitride or even more preferably chromium oxynitride.
  • the multilayer structure can also comprise a single layer C which is deposited between an A single layer and a B single layer, the composition of the C single layer differing from the composition of the A single layer and from the composition of the B single layer, and the C single layer at least contains mostly aluminum chromium oxynitride or preferably chromium oxynitride.
  • Such a C single layer preferably consists of aluminum chromium oxynitride or even more preferably of chromium oxynitride.
  • the multi-layer layer structure comprises, between each individual layer A and each individual layer B, which are alternately deposited one on top of the other, a single layer C, the nitrogen content of which is greater than the nitrogen content in the adjacent individual layer B and less than that Nitrogen content in the adjacent single layer A is.
  • each individual layer A and / or B is preferably between 50 nm and 100 nm.
  • a method for producing an oxidation layer according to the embodiments described above has been disclosed, the method preferably being a PVD method, for example a sputtering method or, for some applications, preferably a spark evaporation method.
  • the process temperature should preferably not be higher than 450 ° C. during the coating process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Chemical Vapour Deposition (AREA)

Claims (4)

  1. Couche de protection contre l'oxydation à base de chrome pour des substrats exposés à des températures élevées, la couche à base de chrome étant appliquée sur un substrat au moyen de PVD et / ou CVD et comprenant un système de couches contenant du chrome, ledit système de couche comprenant une couche de base et une couche fonctionnelle, la couche de base étant entre le substrat et la couche fonctionnelle, la couche fonctionnelle contenant de l'oxyde de chrome, la couche fonctionnelle ayant une structure multicouche comprenant des couches individuelles A et B qui sont déposées en alternance, la composition des couches individuelles A différant de la composition des couches individuelles B, la couche de base étant composée de nitrure de chrome, et les couches individuelles A étant constituées de nitrure de chrome et les couches individuelles B étant constituées d'oxyde de chrome ou d'oxynitrure de chrome,
    caractérisée en ce que, entre chaque couche individuelle A et chaque couche individuelle B, qui sont déposées l'une sur l'autre en alternance, la structure multicouche comprend une couche individuelle C dont la teneur en azote est supérieure à la teneur en azote contenu dans la couche individuelle B directement adjacente et inférieure à la teneur en azote contenu dans la couche individuelle A directement adjacente.
  2. Couche de protection contre l'oxydation selon la revendication 1, l'épaisseur de chaque couche individuelle A et/ou B étant comprise entre 50 nm et 100 nm.
  3. Couche de protection contre l'oxydation selon l'une des revendications précédentes 1 à 2, le rapport entre l'épaisseur de la couche fonctionnelle et l'épaisseur de la couche de base étant compris entre 0,5 et 2 ou entre 0,25 et 1,5.
  4. Procédé de production d'une couche de protection contre l'oxydation selon l'une quelconque des revendications précédentes 1 à 3, le procédé étant un procédé de pulvérisation ou de vaporisation par étincelle, et de préférence une température de procédé non supérieure à 450 ° C est utilisée.
EP14722542.9A 2013-04-16 2014-04-14 Couche de protection contre l'oxydation à base de chrome Active EP2986752B1 (fr)

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US201361812350P 2013-04-16 2013-04-16
PCT/EP2014/000991 WO2014170005A2 (fr) 2013-04-16 2014-04-14 Couche de protection contre l'oxydation à base de chrome

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EP (1) EP2986752B1 (fr)
JP (1) JP7002195B2 (fr)
KR (1) KR102236892B1 (fr)
CN (1) CN105143498B (fr)
AR (1) AR096030A1 (fr)
BR (1) BR112015026344B1 (fr)
CA (1) CA2912584C (fr)
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CN106435489B (zh) * 2016-11-30 2019-01-11 西北有色金属研究院 一种铌基表面抗氧化自愈合Cr/NiCr涂层的制备方法
CN107747093B (zh) * 2017-10-10 2019-10-29 岭南师范学院 一种柔性硬质复合涂层及其制备方法和涂层刀具
EP3714081A1 (fr) 2017-11-24 2020-09-30 Oerlikon Surface Solutions AG, Pfäffikon Revêtements céramiques à base d'al et de cr présentant une stabilité thermique accrue
JP7275449B2 (ja) * 2017-12-22 2023-05-18 エリコン サーフェス ソリューションズ アーゲー、 プフェフィコン ガスタービンのタービンブレードの耐食および耐エロージョンコーティング
EP3768873A4 (fr) * 2018-03-19 2022-06-01 Applied Materials, Inc. Procédés de protection de composants métalliques contre la corrosion au moyen de films minces contenant du chrome
SG11202008268RA (en) 2018-03-19 2020-10-29 Applied Materials Inc Methods for depositing coatings on aerospace components
BR112021009483A2 (pt) * 2018-11-14 2021-08-10 Oerlikon Surface Solutions Ag, Pfäffikon revestimento depositado sobre uma superfície de um substrato e substrato que tem um revestimento
WO2020219332A1 (fr) 2019-04-26 2020-10-29 Applied Materials, Inc. Procédés de protection d'éléments aérospatiaux contre la corrosion et l'oxydation
US11697879B2 (en) 2019-06-14 2023-07-11 Applied Materials, Inc. Methods for depositing sacrificial coatings on aerospace components
CA3208501A1 (fr) * 2021-02-23 2022-09-01 Anders Olof Eriksson Systeme de revetement pour applications de traitement de matiere plastique
CN116145082A (zh) * 2023-03-01 2023-05-23 纳狮新材料有限公司杭州分公司 狭缝涂布模具表面清洗方法及表面结构的制备

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KR102236892B1 (ko) 2021-04-07
CN105143498A (zh) 2015-12-09
CA2912584A1 (fr) 2014-10-23
EP2986752A2 (fr) 2016-02-24
BR112015026344B1 (pt) 2022-05-31
AR096030A1 (es) 2015-12-02
CA2912584C (fr) 2023-07-04
WO2014170005A2 (fr) 2014-10-23
US10174416B2 (en) 2019-01-08
CN105143498B (zh) 2018-11-09
US20160060746A1 (en) 2016-03-03
BR112015026344A2 (pt) 2017-07-25
JP2016520719A (ja) 2016-07-14
KR20160007535A (ko) 2016-01-20
MX2015014649A (es) 2016-06-23
WO2014170005A3 (fr) 2015-03-12
JP7002195B2 (ja) 2022-01-20

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